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Coordination Chemistry Reviews 253 (2009) 30423066

Contents lists available at ScienceDirect

Coordination Chemistry Reviews


journal homepage: www.elsevier.com/locate/ccr

Review

Potential applications of metal-organic frameworks


Ryan J. Kuppler a , Daren J. Timmons b , Qian-Rong Fang a , Jian-Rong Li a , Trevor A. Makal a ,
Mark D. Young a , Daqiang Yuan a , Dan Zhao a , Wenjuan Zhuang a , Hong-Cai Zhou a,
a
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, TX 77842-3012, United States
b
Department of Chemistry, Virginia Military Institute, 303 Science Hall, Lexington, VA 24450, United States

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3043
2. Synthesis and structure of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3043
2.1. Synthetic routes to metal-organic frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3043
2.2. Structural highlights of metal-organic frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3043
3. Hydrogen and methane storage in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3045
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3045
3.2. Hydrogen storage in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3045
3.3. Methane storage in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3048
4. Selective gas adsorption in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3048
4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3048
4.2. Selective gas adsorption in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.2.1. Selective gas adsorption of O2 over N2 based on size-exclusion in rigid MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.2.2. Selective gas adsorption based on size-exclusion in dynamic MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.2.3. Selective gas adsorption based on adsorbatesurface interactions in rigid MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.2.4. Selective gas adsorption based on adsorbatesurface interactions in dynamic MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.3. Useful gas separations in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3049
4.4. MAMS in selective gas adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3050
5. Catalysis in MOFS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3050
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3050
5.2. Catalysis in MOFs with active metal sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3050
5.3. Catalysis in MOFs doped with metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3050
5.4. Catalysis in post-synthesized MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3051
5.5. Selective catalysis in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3051
5.6. Catalysis in chiral MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3053
5.7. Future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3053
6. Magnetic properties of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3053
6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3053
6.2. Magnetic properties of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3054
6.2.1. Ferromagnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3054
6.2.2. Antiferromagnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3055
6.2.3. Ferrimagnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3056
6.2.4. Frustration and canting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3057
6.3. Spin-crossover and induced magnetic change in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3058
7. Luminescence and sensors in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3059
7.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3059
7.2. Luminescence in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3059
7.2.1. Luminescence in MOFs based on metal centers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3059
7.2.2. Luminescence in MOFs based on organic ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3060
7.2.3. Luminescence based on guest molecules in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3060
7.3. Sensors in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3060
7.3.1. Sensors for selective ion monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3060
7.3.2. Sensors for the presence and/or types of guest/solvent molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3061

Corresponding author. Tel.: +1 979 845 4034.

0010-8545/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ccr.2009.05.019
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3043

7.3.3. Sensors for stress-induced chemical detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3061


7.3.4. Sensors for anisotropic photoluminescence probes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3062
8. Drug storage and delivery in MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3062
8.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3062
8.2. Drug-delivery methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3062
8.2.1. Inorganic drug-delivery materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3063
8.2.2. MOF drug-delivery materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3063
8.3. Future work in drug delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3064
9. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3064
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3064
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3064

a r t i c l e i n f o a b s t r a c t

Article history: Metal-organic frameworks have received much attention in recent years especially as newly developed
Received 16 January 2009 porous materials. As such, they possess a wide array of potential applications including materials for gas
Accepted 25 May 2009 storage, gas/vapor separation, catalysis, luminescence, and drug delivery. In the review, these potential
Available online 28 June 2009
applications of metal-organic frameworks are examined and an outlook will be proposed.
2009 Elsevier B.V. All rights reserved.
Keywords:
Metal-organic frameworks
Structure
Potential applications
Applications
Porous materials

1. Introduction 2. Synthesis and structure of MOFs

Porous materials are very useful in gas storage, adsorption- 2.1. Synthetic routes to metal-organic frameworks
based gas/vapor separation, shape/size-selective catalysis, drug
storage and delivery, and as templates in the preparation of low- MOFs are typically synthesized by combining organic ligands
dimensional materials [16]. Traditionally, porous materials have and metal salts in solvothermal reactions at relatively low tem-
been either organic or inorganic materials. Perhaps the most com- peratures (below 300 C). The characteristics of the ligand (bond
mon organic porous material is activated carbon. These are usually angles, ligand length, bulkiness, chirality, etc.) play a crucial role in
prepared by pyrolysis of carbon-rich materials, have high surface dictating what the resultant framework will be. Additionally, the
areas and high adsorption capacities, yet do not possess ordered tendency of metal ions to adopt certain geometries also inuences
structures. Despite this lack of order, porous carbon materials have the structure of the MOF. The reactants are mixed in high boiling,
many uses, including the separation and storage of gases, the puri- polar solvents such as water, dialkyl formamides, dimethyl sulfox-
cation of water, and solvent removal and recovery [7]. ide or acetonitrile. The most important parameters of solvothermal
Inorganic porous frameworks possess highly ordered structures MOF synthesis are temperature, the concentrations of metal salt
(e.g. zeolites). Syntheses often require an inorganic or organic and ligand (which can be varied across a large range), the extent of
template with strong interactions forming between the inorganic solubility of the reactants in the solvent, and the pH of the solution.
framework and the template during the synthesis. As a conse- Although experience often dictates the best conditions for growing
quence, removal of the template can result in collapse of the these crystalline frameworks, experimentation and trial-and-error
framework. Inorganic frameworks also suffer from a lack of diver- methods are still often necessary. Reviews which describe the syn-
sity, as the variation of elements used seldom deviates from Al, thesis and characterization of MOFs have been previously published
Si and chalcogens. Nevertheless, inorganic frameworks have been [1116].
useful in separation and catalysis applications [3]. In addition to this standard method, several other synthetic
In order to take advantage of the properties of both organic methodologies are described in the literature including the mix-
and inorganic porous materials, porous hybrids, known as metal- ture of non-miscible solvents [17], an electrochemical route [18],
organic frameworks (MOFs), can be generated that are both stable and a high-throughput approach [19]. One of the most promising
and ordered and possess high surface areas. It should be noted alternatives is microwave irradiation which allows access to a wide
that MOFs go by many names (porous coordination networks, range of temperatures and can be used to shorten crystallization
porous coordination polymers, etc.) yet all refer to similar if not times while controlling face morphology and particle size distribu-
the same general type of materials. The difference in nomencla- tion [12,20,21]. A serious limitation of this approach is the general
ture merely reects the type of framework and the researchers lack of formation of crystals large enough to obtain good structural
who constructed it. MOFs are essentially coordination polymers data.
formed in the most elementary sense by connecting together
metal ions with polytopic organic linkers often resulting in fas- 2.2. Structural highlights of metal-organic frameworks
cinating structural topologies. These materials have attracted a
great deal of attention in the past decade, and the increase in the When considering the structure of MOFs, it is helpful to recog-
number of papers published in this area during recent years is nize the secondary building units (SBUs), which dictate the nal
remarkable (Fig. 1). Applications in gas storage, gas/vapor sepa- topology of a framework. While the organic linkers are also impor-
ration, size-, shape-, and enantio-selective catalysis, luminescent tant SBUs, their structure seldom changes during MOF assembly.
and uorescent materials, and drug storage and delivery have been The following discussion will focus on metal-cluster-based SBUs,
explored [810]. which result from the initial bonding between the metal ions and
3044 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 1. Number of publications on MOFs over the past decade.

bridging ligands [16]. Fig. 2a and b shows SBUs with a trigonal and a
square planar arrangement of the metal atoms, respectively. Fig. 2c
features a tetrahedron of metal atoms surrounding a central oxo Fig. 3. Looking through the window created by the ligands into the pore (red sphere)
anion, and a dimetal paddlewheel SBU is shown in Fig. 2d. In each of PCN-9 [28]. (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of the article.)
case, the edges between two metal ions are bridged by the coordi-
nating atoms of the ligand and result in control of the orientation
of the linker. general, large pores are advantageous for conducting hostguest
Recently, the geometry of the SBU has been proven to be depen- chemistry such as catalysis, therefore mesoporous (openings
dent on not only the structure of the ligand and type of metal between 20 and 500 ) or even macroporous (openings greater
utilized, but also the metal to ligand ratio, the solvent, and the than 500 ) materials are attractive. Microporous materials have
source of anions to balance the charge of the metal ion [22]. Several pores less than 20 which result in strong interactions between
publications discussed the topic of SBU formation and structure in gas molecules and the pore walls making them good candidates
depth [16,2326]. for gas storage and gas separation applications. In all cases, mea-
Pores are the void spaces formed within MOFs (or any porous surements of these openings are done from atom to atom while
materials) upon the removal of guest molecules (Fig. 3) [27]. In subtracting the van der Waals radii to give the space available for
access by guest molecules.
The pores of MOFs are usually occupied by solvent molecules
that must be removed for most applications. Structural collapse
can occur and, in general, the larger the pore, the more likely the
collapse. Permanent porosity results when the framework remains
intact and is more difcult to achieve in mesoporous MOFs than in
microporous analogues.
Although MOFs can be constructed with ligands designed to gen-
erate large pores, frameworks will often interpenetrate one another
to maximize packing efciency [23]. In such cases, the pores sizes
are greatly reduced, but this may be benecial for some applica-
tions. Indeed interpenetrated frameworks have been intentionally
formed and found to lead to improved performance, for example,
in H2 storage [29].
Following the synthesis, MOFs, like other coordination poly-
mers, may participate in further chemical reactions to decorate
the frameworks with molecules or functional groups in what is
known as post-synthetic modication (PSM) [30]. Sometimes the
presence of a certain functional group on a ligand prevents the
formation of the targeted MOF. In this situation, it is necessary
to rst form a MOF with the desired topology, and then add the
functional group to the framework. This may be applied to MOFs
that are designed for catalysis and gas storage, as these applica-
tions require functional groups to modify the surface property and
pore geometry. It is important to keep in mind that the two most
important factors in PSM are making sure that the reagent used to
enhance the functionality is small enough to t inside the cavity
Fig. 2. Structural representations of several SBUs, including (a) trigonal planar, (b) of the MOF and that the reaction conditions will not destroy the
square planar, (c) tetrahedral, and (d) tetragonal paddlewheel. framework. If the reagent is too small to enter the cavity or the
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3045

framework is destroyed by the reaction, the modication will be which has a BET surface area of 4500 m2 /g and an excess gravi-
useless. metric hydrogen uptake of 7.5 wt% at 70 bar, 77 K [42,43]. However,
when the temperature was raised to ambient temperature, the
hydrogen uptake dropped signicantly, as is the general case. The
3. Hydrogen and methane storage in MOFs
theoretical study from Bhatia and Myers demonstrated that an
adsorption enthalpy change of 15.1 kJ/mol is needed for ambi-
3.1. Introduction
ent temperature storage of hydrogen and delivery between 30
and 1.5 bar of pressure [44]. More importantly, the adsorption
A tank charged with a porous adsorbent enables a gas to be
enthalpy change should be kept at the same level during the
stored at a much lower pressure than an identical tank without an
whole loading range. However, in current MOF-based hydrogen
adsorbent. Thus, high pressure tanks and multi-stage compressors
physisorption, the adsorption enthalpy change is only within the
can be avoided providing a safer and more economical gas storage
range of 410 kJ/mol [13], and the enthalpy drops dramatically
method. Many gas storage studies have been conducted on porous
as the adsorption amount increases. It has become clear that
adsorbents such as activated carbon, carbon nanotubes, and zeo-
increasing the interaction between hydrogen and MOFs is the most
lites [6]. MOFs have received growing attention as such adsorbents
important step towards practical usage of MOF-based hydrogen
due to their tunable pore geometries and exible frameworks. The
storage.
need to reduce global reliance on fossil fuels by the use of alterna-
One way to increase the interaction between hydrogen and
tive technologies has pushed hydrogen and methane gases to the
MOFs is to tailor the pore size in the MOF to maximize the poten-
forefront of gas storage applications. This section will review the
tial overlap of the walls thereby allowing enhanced interaction
state-of-the-art study of hydrogen and methane storage in MOFs.
between hydrogen and MOFs. Theoretical and experimental results
support that the optimal pore size is around 6 , about twice the
3.2. Hydrogen storage in MOFs effective kinetic diameter of the hydrogen molecule [45]. A recent
neutron diffraction study on rare earth MOFs indicated that the
Hydrogen is an ideal energy carrier. It almost triples the gravi- strong interaction between hydrogen and the optimized pore walls
metric heat of combustion of gasoline (120 MJ/kg vs. 44.5 MJ/kg) is comparable to the interaction between hydrogen and unsatu-
[31], and the main byproduct after energy release is water. This rated metal centers, a point which will be discussed later [46].
makes hydrogen a leading candidate for on-board fuel. However, Catenation, when two or more identical frameworks interpene-
hydrogen exists in a gaseous state at ambient temperature and trate each other, could be used to generate MOFs with appropriate
pressure with a density of 0.08 kg/m3 . Even in its liquid state, pore sizes for enhanced hydrogen uptake [36,4750]. There is, how-
which requires pressurizing at a very low temperature (20.27 K), ever, a discrepancy between the theory and experimental results.
the density can only reach 70.8 kg/m3 , one tenth of that of gasoline The grand canonical Monte Carlo (GCMC) simulations done on the
(700 kg/m3 ) [31]. This extremely low volumetric storage den- IRMOF (isoreticular metal-organic framework) series by Ryan et al.
sity presents a hurdle for the practical usage of hydrogen as a proposed that catenation can improve hydrogen uptake in IRMOFs
fuel. In order to guide the research into hydrogen storage, the U.S. at cryogenic temperatures and low pressures, but not at room tem-
Department of Energy (DOE) set gravimetric and volumetric stor- perature [51]. Based on these calculations, there is a temperature
age targets for on-board hydrogen storage for 2010 (6 wt%, 45 g/L) range at which catenation is benecial for hydrogen uptake at low
and 2015 (9 wt%, 81 g/L) [32]. pressures. At higher pressures, however, the non-catenated IRMOFs
Current hydrogen storage techniques involve the use of high adsorb more hydrogen due to a greater free volume (Fig. 4). At ambi-
pressure tanks, cryogenic tanks, chemisorption, and physisorption. ent temperature, catenation does not improve hydrogen uptake for
Pure tank-based hydrogen storage suffers from safety and economic the three IRMOFs studied. Using a template, Ma et al. have gen-
issues [33]. The chemisorption approach allows the formation of erated a pair of catenated and non-catenated MOFs, PCN-6 and
chemical bonds between adsorbed hydrogen and the storage mate- PCN-6 (Fig. 5) [49]. The low pressure and 77 K gas sorption results
rials, leading to greater hydrogen storage density. However, the showed that catenation yields a 41% increase in Langmuir surface
kinetics, reversibility and heat management still remain a problem area and 133% enhancement in volumetric hydrogen uptake (29%
[34]. Physisorption, on the other hand, is based on weak interactions in gravimetric). A further investigation of the effect of catenation
(mainly van der Waals interactions) between the adsorbed hydro- on hydrogen uptake at higher pressure and ambient tempera-
gen and the adsorbent, leading to fast kinetics, full reversibility, and ture shows promising results: 6.7 wt% at 77 K/50 bar (0.92 wt%
manageable heat during hydrogen fueling. However, the promising at 298 K/50 bar) for PCN-6 vs. 4.0 wt% at 77 K/50 bar (0.40 wt% at
data from physisorption-based hydrogen storage are all obtained 298 K/50 bar) for PCN-6 [29]. Inelastic neutron scattering studies
at a cryogenic state (normally 77 K), and the adsorption becomes showed that the interaction between hydrogen and the organic
insignicant at ambient temperature. linkers is stronger in catenated PCN-6 than in non-catenated PCN-
In 2003, Rosi et al. reported the rst MOF-based hydrogen stor- 6 (Fig. 6). This may stem from a greater number of interactions
age study [35]. Subsequently, about 150 MOFs have been tested for from the atoms in the organic ligands, especially at high hydrogen
their hydrogen uptake capacity [13], and several reviews focusing loadings.
on this topic have appeared [13,3641]. In order to avoid repetition, One advantage of using MOFs over other porous materials is that
this section of the review will cover the most current literature and in some MOFs, unsaturated metal centers (UMCs) can be gener-
serve as an update to Ref. [13]. ated by the removal of the coordinated solvent molecules under
Hydrogen storage in MOFs is based on physisorption. It has been vacuum [41]. The interaction between hydrogen and the UMCs is
well established that under physisorption mode, the saturation much higher than that with pure carbon materials, and the isos-
hydrogen uptake at 77 K has a positive correlation with the sur- teric heat of adsorption can sometimes go as high as 1213 kJ/mol
face area of the materials [13,38,40,42]. This is not surprising since [52,53], very close to the projected optimum 15.1 kJ/mol [44]. Lee
increasing the surface area enhances the contact between hydrogen et al. prepared isostructural MOFs with and without UMCs, and
and the adsorbent resulting in an increased hydrogen uptake. compared their hydrogen sorption capacities [54]. MOFs containing
Compared to other porous materials, some MOFs have higher UMCs have higher hydrogen uptake both at low pressure (2.87 wt%
surface areas and subsequently higher hydrogen uptake capac- vs. 2.07 wt% at 77 K/1 atm) and high pressure (5.22 wt% vs. 3.70 wt%
ity. One of the benchmarks is provided by the study on MOF-177, at 77 K/50 bar) than MOFs with saturated metal centers. The higher
3046 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 6. Excess hydrogen sorption isotherms of PCN-6 and PCN-6 at 77 K (red) and
298 K (black): circles, PCN-6; squares, PCN-6 ; solid symbols, adsorption; open sym-
bols, desorption. Reproduced with permission from Ref. [29]. (For interpretation of
the references to color in this gure legend, the reader is referred to the web version
of the article.)

lap inside the void and higher afnity for the subsequent adsorbed
hydrogen.
Theoretical studies revealed that the binding energy between
hydrogen and transition metals can be tuned from about 10 to
50 kJ mol1 by using different transition metals in the MOF sys-
tem [57]. This was partially conrmed by a recent experiment in
which a series of isostructural MOFs were prepared from a vari-

Fig. 4. Simulated hydrogen adsorption isotherms on IRMOFs. Reproduced with per-


mission from Ref. [51].

hydrogen uptake capacity was attributed to the stronger interac-


tion of hydrogen molecules with the UMCs of the MOF, and was
supported by the higher zero-coverage isosteric heat of adsorption
(11.60 kJ/mol vs. 7.24 kJ/mol).
It has been suggested that MOFs with cage-like polyhedral build-
ing units could be useful in the storage of small molecules, because
adsorbed guests may remain kinetically trapped inside the cages
[55]. By linking two isophthalate moieties with the dicopper pad-
dlewheel motif, Wang et al. developed the close-packing strategy
to generate MOFs with polyhedral cage structures and UMCs ratio-
nally aligned to interact directly with the guest inside the void
[56]. The result was encouraging: the MOF with aligned UMCs
(PCN-12) has much higher hydrogen uptake than the misaligned
one (PCN-12 ) (3.05 wt% vs. 2.40 wt%, 77 K/1 atm, Fig. 7). In the
UMCs-aligned-MOF, the initially adsorbed hydrogen around the
UMCs will point into the void, leading to higher potential over-

Fig. 5. (a) Catenated PCN-6. (b) Non-catenated PCN-6 . Reproduced with permission Fig. 7. The synthesis, UMCs alignment, and hydrogen uptake of two MOF poly-
from Ref. [49]. morphs: PCN-12 and PCN-12 . Adapted from Ref. [56].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3047

very limited, and the gravimetric hydrogen uptake capacity was


impaired due to the added mass. Mulfort and Hupp reported the
doping of a catenated MOF with lithium ions by chemical reduc-
tion of the ligand with lithium metal [66]. The lithium-doped MOF
exhibited a 75% increase in gravimetric hydrogen uptake (1.63 wt%
vs. 0.93 wt% at 77 K/1 atm) and a higher heat of adsorption through-
out the entire loading range (65 kJ/mol vs. 5.63.3 kJ/mol). The
extreme enhancement of hydrogen binding (60 H2 molecules per
added Li+ ) was attributed to the direct H2 /cation binding, as well
as other factors such as framework displacement and/or enhanced
strut polarizability.
A further study of the alkali metal cation effects on hydro-
gen uptake and binding in catenated MOFs was carried out using
Li+ , Na+ , and K+ [67]. The 77 K/1 atm gravimetric hydrogen uptake
increase followed as K+ > Na+ > Li+ , while the isosteric heat of
adsorption adopted the opposite trend (Fig. 9). Two observations
cast doubt on the hydrogenmetal binding mechanism: (1) an
extraordinarily large number of hydrogen molecules adsorbed per
dopant cation; and (2) a much smaller isosteric heat of adsorption
Fig. 8. Reaction of Zn4 O(BDC)3 with Cr(CO)6 to generate Zn4 O[(BDC)Cr(CO)3 ]3 (1), compared to the calculated result. More importantly, further doping
followed by photolysis under N2 or H2 to afford Zn4 O[(BDC)Cr(CO)2 (N2 )]3 (3) and with K+ led to decreased hydrogen uptake. After careful examina-
Zn4 O[(BDC)Cr(CO)2 (H2 )]3 (4). Reproduced with permission from Ref. [65].
tion of the nitrogen isotherms, the alkali metal cation effects were
attributed to a molecular-adsorbate-driven displacement of inter-
ety of metal ions (Mg, Mn, Co, Ni, Zn) [58]. The hydrogen sorption woven networks, as well as the possible positioning of the dopant
data showed that within this series the zinc MOF has the lowest ions between the frameworks where they are not readily accessible
heat of adsorption (8.5 kJ/mol) while the nickel one has the high- to hydrogen. More recently it was reported that the metal doping
est (12.9 kJ/mol), and the order of the heat of adsorption matches increased the hydrogen uptake without a signicant change of the
the IrvingWilliams sequence [59] reasonably well. This conrmed heat of adsorption [68]. In order to rule out the effect of framework
previous calculations indicating that the major interaction between displacement in evaluating the doping ions impact on the hydro-
the UMCs and hydrogen molecules is Coulombic attractions [60]. gen uptake, Yang et al. prepared a Li+ -doped MOF by ion exchange
Vitillo et al. studied the role of UMCs in hydrogen storage in MOFs of within a non-catenated MOF [69]. Surprisingly, a 25% increase in
different natures and with different accessibilities of the UMCs [53]. gravimetric hydrogen uptake was observed while the Li+ -doped
Their results indicated that UMCs can increase the binding between MOF displayed a lower isosteric heat for hydrogen adsorption than
hydrogen and MOFs, but their effect in the hydrogen uptake is the original MOF. The increase in hydrogen uptake was attributed to
almost completely hidden in the high pressure range where surface the increase of BET surface area in the Li+ -doped MOF, and, addition-
area and pore volume play primary roles. The efciency of hydro- ally, there was no apparent interaction between adsorbed hydrogen
gen storage by physisorption should increase as the surface density and the exchanged Li+ .
of UMCs is increased. Spillover techniques have been used to further advance hydro-
Many theoretical calculations support the idea that doping gen storage in MOFs. Hydrogen storage by spillover involves the
MOFs with metal ions could enhance the hydrogen uptake capacity split of diatomic hydrogen molecules into hydrogen atoms with
[6164]. This enhancement is proposed to originate from the strong the help of heavy transition metal (e.g. Pd) and the diffusion of
interactions between hydrogen and the doped metal ions. However, the split hydrogen atoms onto the supportive framework (e.g. MOF)
this ideal metal ion geometry adopted in the calculated studies [70]. The initial results of MOF-based hydrogen storage by spillover
is very hard to achieve experimentally. Even though Kaye and Long demonstrated promising capacity and reversibility [71]. Proch et
developed a photosensitive doping method to embed chromium al. embedded Pt into MOF-177 via metal-organic chemical vapor
into MOFs (Fig. 8) [65], additional open coordination sites were deposition and tested the hydrogen uptake capacity at ambient

Fig. 9. Left: 77 K hydrogen isotherm for neutral MOF-1 and metal ion doped-MOF 1 M; Right: isosteric hydrogen heat of adsorption for 1 and 1 M. Reproduced with permission
from Ref. [67].
3048 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

temperature [72]. The rst cycle showed an encouraging 2.5 wt% Unlike for hydrogen, the heat of adsorption for methane (about
hydrogen uptake, but dropped to 0.5 wt% in consecutive cycles. 20 kJ/mol) is already within the ideal scope for practical usage. DOE
The uptake loss was attributed to the formation of metal hydrides, has set a methane storage target: 180 v/v at ambient temperature
which are not desorbed at ambient temperature. and pressure no more than 35 bar [80]. Some of the carbon materials
Ionic MOFs are another proposed approach towards practical have already reached this target [79], but they have limited packing
hydrogen storage in which the binding between hydrogen and density. Thus, the focus has been on increasing the surface area of
MOFs can be enhanced by the attractive electrostatic interactions the porous sorbent.
[7375]. A calculation was performed by Kuc et al. in which the In 1997, Kondo et al. reported the rst methane sorption study
hydrogen molecule was placed in a ctitious linear Na+ H2 Cl using MOFs [81]. Table 1 summarizes the surface area, porosity and
complex, where Na+ and Cl were placed on opposite sides of methane uptake data for selected MOFs. The breakthrough result
hydrogen at a distance of 3.2 from the hydrogen center [76]. The obtained by Ma et al. showed that the methane uptake in a MOF
dipole component at the center hydrogen molecule was calculated can exceed the DOE target [82].
to be 0.73 (0.97) Debye using the NBO (Mulliken) charges; however, One point of concern is that uptake data calculations are based
it is extremely difcult to introduce such a large charge separation on the MOFs crystallographic density, which is higher than the
in real MOF systems. packing density due to the void generated by particle packing [83].
Despite the rapid advancement in MOF research, the DOE hydro- More methane uptake data needs to be calculated from the MOFs
gen storage target has yet to be reached with a pure MOF system. real packing density from MOFs in order to evaluate the potential
However, due to novel properties and well-dened structures, of MOFs in methane storage.
MOFs are still attracting much attention. For example, supercrit-
ical processing in the MOF activation step permits the opening of 4. Selective gas adsorption in MOFs
a gate of even higher surface area [77]. As reported from the high
pressure hydrogen storage study done on IRMOF-1, the upper-limit 4.1. Introduction
hydrogen density based on the physisorption method would hardly
go beyond the density of liquid hydrogen (70.8 g/L) [78]. It was fur- With the ever-increasing demand for cheaper and more environ-
ther concluded that the development of a new method would be mentally friendly industrial applications, new means for selective
necessary to reach DOEs 2015 volumetric hydrogen storage target gas adsorption and separation are being examined. Currently,
(81 g/L). industrial methods for selective gas adsorption rely heavily on cryo-
genic as well as membrane- and adsorption-based techniques. In
3.3. Methane storage in MOFs adsorption-based separation, commonly used adsorbents include
zeolites, molecular sieves, carbon nanotubes, aluminosilicates, and
Natural gas (NG) is another good candidate for on-board fuel. silica gel [8994]. A review of the individual properties and usages
The main component of NG is methane (>95%), while the rest is a in industry of these materials is beyond the scope of this review.
mixture of ethane, other hydrocarbons, nitrogen, and carbon diox- However, all materials for selective gas adsorption are chosen based
ide [79]. Methane has a comparable gravimetric heat of combustion on two main criteria: (1) the adsorption capacity of the adsorbent;
with gasoline (50.0 MJ/kg vs. 44.5 MJ/kg) [31], but it suffers from the and (2) the selectivity of the adsorbent for an adsorbate [2]. These
lack of effective storage. Liqueed natural gas (LNG) can provide properties are dictated by the chemical composition and structure
about 72% of the volumetric energy density of gasoline yet requires of the adsorbent, as well as the equilibrium pressure and temper-
cryogenic conditions (112 K). Compressed natural gas (CNG) can ature during the adsorption. MOFs are very promising candidates
offer about 26% of the volumetric energy density of gasoline but for selective gas adsorption, which can lead to gas separation. In
operates at pressures about 200 bar for compression [79]. Adsorbed particular, mesh-adjustable molecular sieve (MAMS) [95] is such a
natural gas (ANG) provides another storage method in which NG is new type of MOFs that stands out due to its remarkable selectivity
adsorbed on a porous adsorbent, and the volumetric storage energy and tunable properties. A complete review of selective gas adsorp-
density for ANG (at 500 psig) has been reported to be up to 80% of tion and separation in metal-organic frameworks can be found in
that of CNG (at 3000 psig) [79]. Ref. [2].

Table 1
Surface area, porosity, and methane uptake data for selected MOFs.

Materiala Surface area (m2 g1 ) Pore volume (cm3 g1 ) Densityb (g cm3 ) Ambient temperature Hads (kJ mol1 ) Ref.
CH4 uptake
BET Langmuir wt% v/v

Co2 (4,4 -bipy)3 (NO3 )4 1.36 3.6 (30.4 bar) 71 [81]
Cu2 (pzdc)2 (pyz) 1.75 1.3 (31.4 bar) 32 [84]
Cu2 (pzdc)2 (4,4 -bipy) 3.9 (31.4 bar) [84]
Cu2 (pzdc)2 (pia) 4.4 (31.4 bar) [84]
CuSiF6 (4,4 -bipy)2 0.86 9.4 (36.5 bar) 124 [85]
Zn4 O(R6 -bdc)3 IRMOF-6 2630 0.60 0.65 14.7 (36.5 bar) 155 [86]
MIL-53(Al) Al(OH)(bdc) 1100 1590 0.59 0.98 10.2 (35 bar) 155 17 [87]
MIL-53(Cr) Cr(OH)(bdc) 1100 1500 0.56 1.04 10.2 (35 bar) 165 17 [87]
PCN-14 Cu2 (adip) 1753 0.87 0.83 16.0 (35 bar) 220 30 [82]
PCN-11 Cu2 (sbtc) 1931 2442 0.91 0.75 14.1 (35 bar) 171 14.6 [88]
HKUST-1 Cu3 (btc)2 1502 2214 0.76 0.88 15.7(150 bar) 228 [83]
Zn2 (bdc)2 dabco 1448 2104 0.75 0.87 14.3 (75 bar) 202 [83]
MIL-101 Cr3 FO(bdc)3 2693 4492 1.303 0.31 14.2 (125 bar) 72 [83]
a
4,4 -bpy = 4,4 -bipyridine, pzdc = pyrazine-2,3-dicarboxylate, pyz = pyrazine, pia = N-(pyridin-4-yl)isonicotinamide, R6 -bdc = 1,2-dihydrocyclobutabenzene-
3,6-dicarboxylate, dbc = benzenedicarboxylate, adip = 5,5 -(9,10-anthracenediyl)di-isophthalate, abtc = azobenzene-3,3 ,5,5 -tetracarboxylate,
 
sbtc = trans-stilbene-3,3 ,5,5 -tetracarboxylate, btc = benzene-1,3,5-tricarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane.
b
Calculated from single crystal structure without guest molecule and labile ligand binding.
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3049

nation sites, leading to high afnity for O2 . This MOF can adsorb
14 mmol of O2 but only 3 mmol of N2 [100].

4.2.4. Selective gas adsorption based on adsorbatesurface


interactions in dynamic MOFs
The adsorbentguest interactions in dynamic MOFs have also
demonstrated adsorption selectivity of O2 over N2 [99,101103].
Depending on the interaction between the adsorbate and the adsor-
bent, pore expansion or constriction also occurs. This is known as
the gate-opening process [2]. Characteristic gate-opening selective
adsorption of O2 over N2 has been observed in Cd(bpndc)(4,4 -bpy),
in which approximately 150 mL/g of O2 was adsorbed with almost
no N2 uptake [103]. This signicant difference in gas uptakes was
attributed to the interaction of the O2 molecules with the frame-
work, which is stronger than that of N2 . Similar results have been
Fig. 10. Hydrogen, oxygen, nitrogen, and carbon monoxide adsorption isotherms of shown with Cu(dhbc)2 (4,4 -bpy) and Cu(bdc)(4,4 -bpy)0.5 but with
PCN-13 at 77 K. Reproduced with permission from Ref. [96].
less uptake of O2 [101,102].

4.2. Selective gas adsorption in MOFs


4.3. Useful gas separations in MOFs
The principal mechanisms based on which selective gas adsorp-
The separation of alkane isomers from natural gas is of primary
tion is achieved in MOFs are adsorbatesurface interactions and
concern for industrial applications. It has been demonstrated that
size-exclusion (molecular sieving effect). The former involves the
MOF-508 may be utilized to separate such alkanes using gas chro-
chemical and/or physical interaction between the adsorbent and
matographic techniques [104]. The 3D pillared layer provides the
the adsorbate while the latter depends on the dimension and shape
necessary framework to selectively separate linear and branched
of the framework pores. It is important to keep in mind that the
alkanes by adsorbing the linear ones while allowing the branched
two effects are capable of working independently as well as coop-
alkanes to pass because of the difference in van der Waals inter-
eratively.
actions between the isomers and the frameworks pores [105].
Additionally, this MOF proved effective in separating natural gas
4.2.1. Selective gas adsorption of O2 over N2 based on mixtures through gas chromatography.
size-exclusion in rigid MOFs Recently, MOFs have been incorporated into thin-lm materi-
Selective gas adsorption based on size-exclusion principle als to aid in gas separation. The copper net supported Cu3 (btc)2
has been successfully demonstrated with several MOFs. PCN- MOF thin lm developed by Guo et al. demonstrated the successful
13 (Zn4 O(H2 O)3 (C16 H8 O4 )3 2DMF) contains a square hydrophobic separation of H2 from H2 /N2 , H2 /CO2 , and H2 /CH4 mixtures [106].
channel of 3.5 3.5 and has a pore volume of 0.3 cm3 /g [96]. This MOF demonstrated excellent permeation selectivity for H2 and
The larger size of the N2 molecule (kinetic diameter of 3.64 ) possessed separation factors much higher than traditional zeolites
as opposed to the O2 molecule (kinetic diameter of 3.46 ) com- (Fig. 11). The recyclability of this MOF further enhances its potential
pletely prevents N2 from entering the aperture while allowing for application in H2 separation and purication.
O2 to pass through the pore as shown in Fig. 10. Likewise, Recently, Couck et al. demonstrated the successful separation of
Mg3 (ndc)3 , with its pore opening of approximately 3.463.64 , CO2 and CH4 gases using amino-functionalized MIL-53(Al) [107].
demonstrates almost no N2 uptake at 77 K and 880 Torr whereas Because CO2 possesses a quadrupole moment, the CO2 molecules
approximately 3.5 mmol/g of O2 is adsorbed [97]. PCN-17 (Yb4 (4 - have a high afnity for the amino groups. Breakthrough experi-
H2 O)(C24 H12 N3 O6 )8/3 (SO4 )2 3H2 O10DMSO), with its large cages ments demonstrated that the weakly adsorbed CH4 is able to pass
connected by small apertures, is able to selectively adsorb over ten through a MOF-packed column while CO2 is adsorbed. Thus, ef-
times as much O2 as N2 [98]. cient separation of the two gases can be performed at ambient
conditions, as shown in Fig. 12.
4.2.2. Selective gas adsorption based on size-exclusion in
dynamic MOFs
The cases in the foregoing discussion involve MOFs that are
classied as rigid and do not display any obvious exible behav-
ior. Dynamic, or exible MOFs exist and their applications depend
not only on the size of the aperture, but also on adsorption con-
ditions (pore sizes vary with pressure/temperature adjustment
and/or are controlled by hostguest induced gate opening) [2].
Nevertheless, the adsorption selectivity of O2 over N2 , based
mainly on size-exclusion in dynamic MOFs, has also been observed.
Ni2 (cyclam)2 (mtb) can selectively adsorb O2 because its interpen-
etrated network results in narrow channels that are only large
enough for O2 molecules to pass through [99].

4.2.3. Selective gas adsorption based on adsorbatesurface


interactions in rigid MOFs
Adsorbatesurface interactions also play a very important role
in the selective gas adsorption of O2 over N2 . For example, the pore Fig. 11. The separation factors for various H2 gas mixtures by copper net supported
walls of the rigid MOF Cu(bdt) contain unsaturated metal coordi- Cu3 (btc)2 MOF thin lm. Reproduced with permission from Ref. [106].
3050 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

lene, butane, and, theoretically, any gas that has a kinetic diameter
between 2.9 and 4.6 .

5. Catalysis in MOFS

5.1. Introduction

As porous materials, MOFs may prove to be very useful in


catalysis. Theoretically, the pores of MOFs can be tailored in a
systematic way allowing optimization for specic catalytic applica-
tions. Besides the high metal content of MOFs, one of their greatest
Fig. 12. Separation of CO2 and CH4 gas mixtures using amino-MIL-53(Al). Repro-
duced with permission from Ref. [107]. advantages is that the active sites are rarely different because of
the highly crystalline nature of the material. Although catalysis is
one of the most promising applications of such materials, only a
4.4. MAMS in selective gas adsorption few examples have been reported to date. In these MOFs, size- and
shape-selective catalytic applications depend on porosity and the
One of the most promising materials for selective gas adsorp- presence of catalytically active transition-metal centers.
tion is the MOF-based mesh-adjustable molecular sieve [95]. MAMS
are very useful when attempting to separate gases in which the 5.2. Catalysis in MOFs with active metal sites
difference in size is very small. Unlike in more rigid systems, the
pore sizes in MAMS can be tuned across a wide array by simply Zou et al. have prepared a 3D functional MOF by using a
adjusting the temperature (Fig. 13). Such a material has recently discrete metalorganic cubic building block [Ni8 L12 ]20 (H3 L = 4,5-
been reported by Ma et al. as MAMS-1, a layered structure with imidazoledicarboxylic acid) bridged by alkali-metal ions (Na+ )
hydrophilic channels and hydrophobic chambers interconnected [111]. This MOF exhibited stable catalytic activity for the oxidation
through a size-adjustable gate [95]. In MAMS-1, the hydrophobic of CO to CO2 . Fig. 14b shows the rate of CO oxidation, RQMS , obtained
chambers are the site of gas storage, yet the gas must rst pass by quadrupole mass spectroscopy in comparison with those for
through the hydrophilic channels. Between the hydrophilic chan- NiY zeolite and nickel oxide (NiO).
nels and the hydrophobic chambers lie two bbdc ligands that serve Gndara et al. obtained a new In(III) MOF composed of
as the gate that can be opened or closed with an increase or decrease thick layers containing square-shaped channels (Fig. 14a) [112].
in temperature, respectively. By simply varying the temperature The channels are empty in In(OH)L and lled with pyridine
between 60 and 300 K, the gate size of MAMS-1 can be adjusted any- in [In(OH)L]xPy (L = 4,4 -(hexauoroisopropylidene)bis(benzoic
where from 2.9 to 5.0 . Thus, fractional adsorption may be attained acid)). This microporous, thermally stable compound has been
on MAMS-1 for separation of virtually any multi-component gas so proven to be an efcient heterogeneous catalyst for acetalization
long as the target molecules kinetic diameter falls within this range. of aldehydes (Fig. 14b). The difference in catalytic activity between
Industry-relevant experiments have been carried out on MAMS-1 compounds with empty or lled channels demonstrates that catal-
and have demonstrated selective adsorption of H2 over CO2 , O2 , ysis does indeed take place inside the pores.
and N2 at 77 K; O2 over CO and N2 at 87 K; N2 over CO2 and CH4
at 113 K; CH4 over C2 H4 at 143 K; C2 H4 over C3 H6 at 196 K; C3 H6 5.3. Catalysis in MOFs doped with metal catalysts
over iso-C4 H10 at 241 K [95]. In addition, the MOFs Mn(HCOO)2 and
Cu(etz) also exhibit temperature-dependent gate-opening behavior Recently, Eddaoudi and co-workers have demonstrated the uti-
[108,109]. lization of In-HImDC-based rho-ZMOF (Fig. 15a) as a host for large
Isostructural MAMSs (MAMS-2, MAMS-3, and MAMS-4, pre- catalytically active molecules, specically metalloporphyrins, and
pared with metal centers of Zn, Co, and Cu, respectively) also its effect on the enhancement of catalytic activity [113]. To produce
display temperature-dependant molecular sieving effects [110]. a versatile platform, they encapsulated the free-base porphyrin
Like MAMS-1, a linear relationship exists between temperature and which was readily metallated and post-synthetically modied by
mesh size, with the new MAMSs mesh size existing anywhere from various transition metal ions to produce a wide range of encap-
2.9 to 4.6 when the temperature is adjusted from 77 to 273 K. As sulated metalloporphyrins. Hydrocarbon oxidation was performed
temperature increases, the van der Waals interactions between the in the presence of Mn-RTMPyP (5,10,15,20-tetrakis(1-methyl-
tert-butyl groups of the ligands of the framework decrease, thus 4-pyridinio)porphyrin tetra(p-toluenesulfonate encapsulated in
allowing larger molecules to pass through the frameworks gate. rho-ZMOF) to assess catalytic activity for cyclohexane oxidation
This selectivity provided selective adsorption of O2 , N2, CO, ethy- (Fig. 15b).

Fig. 13. The structure of MAMS-1 and the pore opening dependence on temperature. Reproduced with permission from Ref. [2].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3051

Fig. 14. (a) Polyhedral representation of the structure. (b) Acetalization catalyzed by [In(OH)L]0.5Py (white columns) and [In(OH)L] (black columns). Reproduced with
permission from Ref. [112].

The embedding of Ru nanoparticles in the otherwise unchanged were generated by simply treating the porous, homochiral MOFs
metal-organic framework MOF-5 has been investigated by Schrder with HCl in diethyl ether. Containment within the MOF pore wall is
et al. (Fig. 16) [114]. After the inclusion of Ru to form crucial and no homogeneous analogues are known.
[Ru(cod)(cot)]3.5 @MOF-5, hydrogenolysis formed Ru nanoparticles
inside the cavities and lead to the material Ru@MOF-5. Prelimi- 5.5. Selective catalysis in MOFs
nary results for alcohol oxidation with Ru@MOF-5 revealed limited
catalytic applications of the water-sensitive MOF-5 host material. Kitagawa and co-workers successfully synthesized a 3D porous
coordination polymer (PCP) functionalized with amide groups,
5.4. Catalysis in post-synthesized MOFs ([Cd(4-btapa)2 (NO3 )2 ]6H2 O2DMF)n , from the reaction between
Cd(NO3 )2 4H2 O and a three connector-type amide ligand (4-btapa)
Hwang et al. found that the presence of chromium(III) [117]. The amide groups are ordered uniformly on the channel
coordinatively unsaturated metal sites (CUSs) in chromium(III) surfaces (Fig. 19a) and facilitate the selective accommodation and
terephthalate MIL-101 can provide an intrinsic chelating property activation of guests within the channels. Knoevenagel condensation
with electron-rich functional groups that leads to the formation of reactions of benzaldehyde with active methylene compounds (e.g.
the thermally stable amine species grafted to the surface (Fig. 17) malononitrile, ethyl cyanoacetate, and cyano-acetic acid tert-butyl
[115]. This feature offers a powerful way to selectively function- ester) were conducted (Fig. 19b). While malononitrile proved to be
alize the unsaturated sites in MIL-101. It was demonstrated that a good substrate (98% conversion), the other substrates produced
ethylenediamine and diethylenetriamine can be used as new graft- negligible results implicating a relationship between the size of the
ing agents to produce the amine-grafted MIL-101, which exhibit reactants and the pore window of the host.
remarkably high activities in the Knoevenagel condensation. Addi- The catalytic activity of the sodalite-type compound
tionally, palladium loaded APS-MIL-101 and ED-MIL-101 have high Mn3 [(Mn4 Cl)3 (BTT)8 (CH3 OH)10 ]2 has been investigated by Long et
activities during the Heck reaction (393 K), a powerful reaction used al. The compound is a thermally stable microporous solid exhibit-
to couple alkenes with organic moieties. ing a cubic network of 7 and 10 pores that affords a BET surface
Recently Ingleson et al. reported the rational, post-synthetic area of 2100 m2 g1 [118]. The surface contains exposed Mn2+ ions
modication of a series of MOFs, M(asp)L0.5 (M = Ni2+ or Cu2+ , that serve as Lewis acids (Fig. 20). Indeed, this compound catalyzes
asp = L-aspartate or D-aspartate, L = bipy or bpe) (Fig. 18) [116]. The the cyanosilylation of aromatic aldehydes and ketones, as well as
protonated frameworks needed to conduct acid-catalyzed reactions the more demanding Mukaiyama-aldol reaction. Moreover, in each

Fig. 15. (a) Crystal structure of rho-ZMOF (left) and schematic presentation of [H2 TMPyP]4+ porphyrin ring enclosed in rho-ZMOF R-cage (right, drawn to scale). (b) Cyclohexane
catalytic oxidation using Mn-RTMPyP as a catalyst at 65 C. Reproduced with permission from Ref. [113].
3052 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 16. Model of the inclusion compound [Ru(cod)(cot)]3.5 @MOF-5. Reproduced with permission from Ref. [114].

Fig. 17. Site-selective functionalization of MIL-101 with unsaturated metal sites: (A) perspective view of the mesoporous cage of MIL-101 with hexagonal windows; (B, C)
evolution of coordinatively unsaturated sites from chromium trimers in mesoporous cages of MIL-101 after vacuum treatment at 423 K for 12 h; (D) surface functionalization of
the dehydrated MIL-101 through selective grafting of amine molecules onto coordinatively unsaturated sites; (E) selective encapsulation of noble metals in the amine-grafted
MIL-101 via a three-step process. Adapted from Ref. [115].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3053

Fig. 18. Left, Cu(asp) 2D layer dashed red lines emphasise JahnTeller elongated CuO bonds. Right, cross-sectional view down the a axis (solvent removed for clarity)
displaying the 1D porous channels between chiral Cu(asp) layers. Reproduced with permission from Ref. [116]. (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of the article.)

Fig. 19. (a) Crystal structure to form another type of zigzag channels with dimensions of 3.3 3.6 . (b) Knoevenagel condensation reaction of benzaldehyde with substrates.
Reproduced with permission from Ref. [117].

case, a pronounced size-selectivity effect consistent with the pore excess Ti(Oi Pr)4 in toluene led to an active catalyst for the addition
dimensions is observed. of diethylzinc to aromatic aldehydes to afford chiral secondary
alcohols upon hydrolytic workup. Chiral secondary alcohols were
5.6. Catalysis in chiral MOFs generated by this MOF in very high yields and enantioselectivities.
For example, the addition of diethylzinc to 1-naphthaldehyde was
In 2000, Seo et al. [119] reported the synthesis of a homochi- catalyzed to afford (R)-1-(1-naphthyl)-propanol with complete
ral metal-organic porous material, [Zn3 (3 -O)(L)6 ]2H3 O12H2 O conversion and 90.0% ee.
(referred to as D-POST-1, L = D-tartaric acid), which uses enantiop-
ure metal-organic clusters as secondary building blocks (Fig. 21a). 5.7. Future research
The presence of the pyridyl groups exposed in the channels also
provides POST-1 with unique opportunities in catalysis. The cat- Future research should be dedicated to elucidate whether the
alytic transesterication of ethanol occurred in 77% yield with metal centers, the ligands, particle size, or some combination of
POST-1 (Fig. 21b). The transesterication with bulkier alcohols such these can engender MOFs with unusual catalytic properties. More
as isobutanol, neopentanol and 3,3,3-triphenyl-1-propanol using work is needed to determine if MOFs can compete with well-known
transesterication occurred at a much slower or even negligible heterogeneous industrial catalysts.
rate under otherwise identical reaction conditions (Fig. 21c).
Wu and Lin synthesized a homochiral porous MOF, 6. Magnetic properties of MOFs
[Cd3 L4 (NO3 )6 ]7MeOH5H2 O (L = (R)-6,6 -dichloro-2,2 -dihydroxy-
1,1 -binaphthyl-4,4 -bipyridine), by slow diffusion of diethyl ether 6.1. Introduction
into a mixture of Cd(NO3 )2 4H2 O and (R)-6,6 -dichloro-2,2 -
dihydroxy-1,1 -binaphthyl-4,4 -bipyridine in DMF/CHCl3 /MeOH at Magnets are very important materials with an ever-increasing
room temperature (Fig. 22) [120]. Treatment of this compound with number of uses. Thus, an important goal of the research of mag-
3054 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

between the paramagnetic metal ions or organic radicals through


diamagnetic bridging entities. Therefore, their magnetic behaviors
depend on the intrinsic nature of both the metal and the organic
ligand as well as the particular level of organization created by
the metalligand coordination interaction. As a result, in pursu-
ing the magnetism of MOFs, the ligand design is crucial both to
organize the paramagnetic metal ions in a desired topology and to
efciently transmit exchange interactions between the metal ions
in a controlled manner. The formation of a bulk material with non-
zero spin requires a framework that allows for parallel coupling of
the spins of neighboring paramagnetic spin carriers or antiparal-
lel coupling of unequal spins. Canted spin orientations may also
result. It should be pointed out that there is always a tendency for
antiparallel coupling of spins because the state of low-spin multi-
plicity is often more stable than the state of high-spin multiplicity
[122].
Magnetic studies of MOFs are embedded in the area of molecu-
lar magnets and the design of low-dimensional magnetic materials,
magnetic sensors, and multifunctional materials. Indeed, closed-
shell organic ligands that are typically used in MOFs mostly give rise
to only weak magnetic interactions. In order to achieve a strong cou-
pling between the metal centers, short oxo, cyano, or azido bridges
are needed [123125]. Alternatively, polymeric metal cyanide com-
pounds are frequently encountered in magnetic investigations but
fall outside the scope of this review. Furthermore, the porosity
of MOFs provides additional interesting phenomena in regards to
magnetic properties. The use of chemical coordination or crystal
engineering techniques allows for the systematic design of MOFs
with adjustable magnetic properties. Because the magnetic prop-
erties of MOFs have been recently reviewed [122,126128], this
section will give only a brief enumeration of recent results in the
investigations of magnetic MOFs.

6.2. Magnetic properties of MOFs

6.2.1. Ferromagnetic properties


Ferromagnetism requires a structure that allows for parallel cou-
pling of the spins. There are numerous reports about the magnetic
Fig. 20. A portion of the crystal structure showing the two different types of MnII properties of MOFs; however, literature on ferromagnetic MOFs is
sites exposed within its three-dimensional pore system of 10 wide channels. Site I still limited. Biswas et al. [129] reported a magnetic MOF material,
is ve-coordinate, while site II is only two-coordinate; the separation between them
{[Cu2 (pic)3 (H2 O)]ClO4 }n (pic = 2-picolinate), which is constructed
is 3.420(8) . Reproduced with permission from Ref. [118].
by sh backbone chains through syn-anti carboxylate groups.
These chains are linked to one another by syn-anti carboxylate
netic materials is the improvement of the properties of magnets as groups to give rise to a rectangular grid-like 2D net as shown in
well as exploring new functions, in particular in combination with Fig. 23a. The ClO4 anions are located between these 2D cationic
other useful phenomena [121]. The magnetic properties such as sheets. Magnetic susceptibility measurements revealed the pres-
ferromagnetism, antiferromagnetism, and ferrimagnetism of poly- ence of weak ferromagnetic coupling for this MOF that has been
metallic systems derive from the cooperative exchange interactions tted with a suitable model (Fig. 23b).

Fig. 21. (a) The hexagonal framework with large pores that is formed with the trinuclear secondary building units. (b) Catalytic activity of POST-1 in transesterication
reactions with ethanol, and (c) with different alcohols. Reproduced with permission from Ref. [119].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3055

Fig. 22. (a) The 2D square grid in the crystal structure and (b) space-lling model as viewed down the c axis showing the chiral 1D channels of 13.5 13.5 in dimensions.
Reproduced with permission from Ref. [120].

Fig. 23. (a) 2D layer [1 1 0] of the CuII -picolinate-bridged structure in {[Cu2 (pic)3 (H2 O)]ClO4 }n . (b) Thermal variation of the product of the molar magnetic susceptibility and
temperature (m T) for {[Cu2 (pic)3 (H2 O)]ClO4 }n . Reproduced with permission from Ref. [129].

Another interesting example is TTTACu(hfac)2 , an adduct of a interchain interactions. Thus, the magnetic properties were inter-
metal complex and an organic free radical, reported by Fujita and preted in terms of a ferromagnetic dimer with a weak inter-dimer
Awaga [130]. In this structure TTTA ligands bridge Cu2+ ions to result antiferromagnetic interaction.
in zigzag chains along the b axis, which are assembled together
by two short contacts between the S atom on the dithiazolyl ring 6.2.2. Antiferromagnetic properties
and the O atoms of Cu(hfac)2 to form a 2D supramolecular layer Many MOFs have antiferromagnetic properties due to the
(Fig. 24a). The magnetic measurements showed a ferromagnetic antiparallel coupling of the spin metal ions or the organic free
coupling ascribed to the coordination bond between Cu(hfac)2 and radical entities. Recently, Jia et al. [131] reported a 3D Mn2+ frame-
TTTA and a weak antiferromagnetic coupling at low temperature work, Mn2 (tzc)2 (bpea), in which 2D layers with 3 -tzc bridges are
due to the weak interaction between Cu(hfac)2 and TTTA and/or the pillared by the bpea spacers to generate a 3D structure with a 3,4-

Fig. 24. (a) A view of the structure of TTTACu(hfac)2 . The CF3 groups of Cu(hfac)2 are omitted for clarity. The interchain contacts are shown by the broken lines. (b) Temperature
dependence of p T for TTTACu(hfac)2 . Reproduced with permission from Ref. [130].
3056 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 25. The extended structure of Mn2 (tzc)2 (bpea). (a) A 2D layer with tzc as 3 -bridging ligands, (b) the 2D topology, (c) the 3D structure, and (d) the 3D topology with
self-catenation highlighted by bold lines. Reproduced with permission from Ref. [131].

connected self-penetrating topology of (482 103 )(482 ) (Fig. 25). to form a non-interpenetrated (10, 3)-a framework containing
The magnetic measurements revealed antiferromagnetic coupling chiral channels (Fig. 26a). Magnetic susceptibility measurements
between Mn2+ ions in this framework. indicated that this MOF exhibited paramagnetic properties within
Yu et al. [132] also characterized the magnetic behav- measured temperature range 2300 K, though antiferromagnetic
ior of a non-interpenetrating chiral porous cobalt MOF, coupling existed between neighboring Co2+ atoms (Fig. 26b).
Co3 (TATB)2 (H2 O)2 2DMA3H2 O. The framework is composed
of a trimetallic hourglass cluster linked by organic ligands with 6.2.3. Ferrimagnetic properties
the cluster being responsible for the magnetic properties of the In MOFs, the exchange coupling among paramagnetic centers
MOF. In the framework, every ligand pair is bound to three Co2+ typically leads to ferromagnetic or antiferromagnetic behavior,
clusters and every cluster connects with three ligand pairs to form resulting in very few instances of ferromagnetic behavior. Usu-
a propeller. The clusters are extended by the TATB ligand pairs ally, the ferrimagnetic systems contain two kinds of spin carriers

Fig. 26. (a) 3D framework structure of Co3 (TATB)2 (H2 O)2 . (b) Susceptibility as function of temperature (inset shows the 1/ vs. T curve along with a theoretical tting).
Reproduced with permission from Ref. [132].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3057

Fig. 27. (a) 3D framework structure of Cu3 (L)2 (VO3 )4 . (b) m T vs. T plot at different elds and the zero eld cooled (ZFC) and eld cooled (FC) susceptibility plot for Cu3 (L)2 (VO3 )4 .
Reproduced with permission from Ref. [133].

that alternate regularly and interact antiferromagnetically [121]. In press or signicantly reduce long-range magnetic ordering and
contrast, homospin ferrimagnetic systems contain only one type may lead to unusual ground-state behaviors. The magnetic frustra-
of spin carrier that, in spite of the antiferromagnetic coupling, tions are usually observed in triangular or tetrahedral plaquette
leads to a non-cancellation of spins as a result of a partic- magnetic lattices [134136]. Gao et al. [137] recently reported a
ular topological arrangement of the spins. Recently, Li et al. Mn2+ complex, Mn[Mn3 (3 -F)(bta)3 (H2 O)6 ]2 which has a 2D frus-
[133] reported a 3D homospin ferrimagnet, Cu3 (L)2 (VO3 )4 (L = 5- trated lattice with alternating triangular motifs and mononuclear
(pyrimidin-2-yl)tetrazolate) constructed from (VO3 )n chains link- centers. Magnetic studies showed this compound to behave as a
ing ([5-(pyrimidin-2-yl)tetrazolate-(Cu2+ )1.5 ]2+ )n layers (Fig. 27a). low-temperature antiferromagnet (Fig. 28). The stoichiometry and
In the structure, there exist two crystallographically independent connecting mode of the mono- and tri-nuclear Mn2+ moieties in the
Cu2+ centers that are responsible for the unusual magnetic property. 2D lattice led to an uncompensated spin moment, which caused the
Magnetic measurements revealed this complex to be a ferrimagnet frustration.
with TN = 10 K (Fig. 27b). This framework can be seen as two lattices In contrast to ferrimagnetism, residual spin resulting from per-
with an antiferromagnetic coupling between them that results in turbation of antiparallel or parallel coupling may induce spin
an uncompensated spin S = 1/2 per every three Cu2+ atoms. At low canting. Asymmetric exchange interactions and single-ion mag-
temperatures the uncompensated spins align parallel to each other, netic anisotropy are the origins of this magnetic behavior [138].
resulting in the ferromagnetic long-range order. Several MOFs have presented spin canted antiferromagnetic prop-
erties. Li et al. [139] reported a CoII MOF, Co2 (L)2 (H2 O)2 (L = 2,1,3-
6.2.4. Frustration and canting thiadiazole-4,5-dicarboxylate), which has a non-interpenetrated
Frustrated magnetic materials have attracted much attention (10,3)-d (utp) topological network structure. It is interesting that
because the competing interactions in these materials can sup- in the crystallographic asymmetric unit there exist two unique

Fig. 28. Left: views of the structure of Mn[Mn3 (3 -F)(bta)3 (H2 O)6 ]2 , showing (a) coordination environments of the metal ion and the ligand, (b) the 2D layer, and (c) the
3,6-connected net of the layer. Right: (a) temperature dependence of the susceptibility of Mn[Mn3 (3 -F)(bta)3 (H2 O)6 ]2 . Inset: FC (20 and 1000 Oe) and ZFC (20 Oe) plots,
(b) eld-dependent magnetization, (c) schematic illustration of the 2D lattice, (d) a segment of the lattice illustrating the frustration and the triangular sublattice of Mn.
Reproduced with permission from Ref. [137].
3058 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 29. Left: view of the 3D framework structure of Co2 (L)2 (H2 O)2 (un-coordinated carboxylate O atoms and water molecules were omitted for clarity). Right: (a) m T vs. T
plot for Co2 (L)2 (H2 O)2 (insert: plot of the reduced magnetization at 2 K), (b) hysteresis loop, (c) m T vs. T plots at different elds (from 1000 to 50 G) in the low-temperature
region, (d) plot of the ac susceptibility. Reproduced with permission from Ref. [139].

but chemically similar Co2+ ions, which were linked by ligands 6.3. Spin-crossover and induced magnetic change in MOFs
to form a 3D framework (Fig. 29, left). These two crystallograph-
ically different CoII ions were determined to be responsible for Among efforts to introduce specic functions to MOFs, the
the magnetic behaviors. Magnetic measurements showed that this incorporation of electronic switching centers is very important
complex takes on unexpected long-range magnetic ordering as in the development of new advanced functional materials for
shown in Fig. 29, right. Due to the shape of the m T curve, ferromag- molecular-scale switching devices. Spin-crossover centers repre-
netic coupling between the Co2+ ions does not seem likely at high sent a convenient, addressable molecular-scale magnetic switch
temperatures. There are different magnetic pathways Co1Co2, in which d4 d7 transition metals can change between the high-
Co1Co1, and Co2Co2 that have to be antiferromagnetic unless spin and low-spin state in response to variation in temperature,
the syn-anti carboxylate coordinate mode is ferromagnetic yet pressure, or light irradiation [140]. Recently, Halder et al. [141]
very small in magnitude. Thus, the origin of this magnetic order reported a nanoporous MOF, Fe2 (azpy)4 (NCS)4 (guest) which has
can be attributed to a weak magnetic ordering, the so-called an interpenetrated 2D layer to 3D framework structure contain-
canting. ing electronic switching Fe2+ centers and displays reversible uptake

Fig. 30. (a) The structures of Fe2 (azpy)4 (NCS)4 (EtOH) at 150 and 375 K. (b) The temperature-dependent magnetic moment of Fe2 (azpy)4 (NCS)4 (guest), recorded on a single
sample at different stages of guest desorption and resorption, showing 50% spin-crossover behavior between 50 and 150 K for the fully loaded phases and an absence of
spin-crossover for the fully desorbed phase. The ethanol and methanol-loaded phases undergo a single step spin-crossover, whereas the 1-propanol adduct shows a two-step
crossover with a plateau at 120 K. The inset shows the effect of partial and complete removal of methanol from Fe2 (azpy)4 (NCS)4 (MeOH). Reproduced with permission from
Ref. [141].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3059

Fig. 31. (a) Structure of Cu3 (PTMTC)2 (py)6 . (b) Reversible magnetic behavior of the amorphous and evacuated phase in contact with ethanol liquid, as observed by plotting
T as a function of temperature T at a eld of 1000 Oe. Inset: similar behavior at 10,000 Oe. Reproduced with permission from Ref. [143].

and release of guest molecules (Fig. 30a). The exibility from the 7. Luminescence and sensors in MOFs
interpenetrated framework allows guest uptake and release, which
in turn causes substantial changes in the local geometry at the Fe2+ 7.1. Introduction
centers. As a result, the presence of Fe2+ spin-crossover centers
within the framework lattice led to the switching of this material: The potential use of MOFs as luminescent materials has spurred
the sorbed phases undergoing half-spin crossovers, and the des- much interest in the area [144,145]. These materials can be prepared
orbed phase showing no switching property (Fig. 30b). This work by combining the luminescent metal ions or clusters and organic
has shown that MOF materials can incorporate an additional level of ligands, as well as special guest molecules [146].
functionality, such as spin-transition associated with their porous
natures to produce new, useful properties. Furthermore, the pho- 7.2. Luminescence in MOFs
tomagnetic properties of a similar porous Fe2+ spin-crossover MOF,
Fe(NCS)2 (bped)2 3EtOH has been investigated by the same group 7.2.1. Luminescence in MOFs based on metal centers
[142]. Lanthanide metal ions have been widely used in MOF syn-
Solvent-induced magnetic properties have also been observed theses due to their coordination diversity and luminescent
in a nanoporous MOF structure, Cu3 (PTMTC)2 (py)6 (EtOH)2 (H2 O), properties. Chandler et al. [147] reported a stepwise approach
which was constructed by using a persistent organic free rad- to synthesizing a MOF with photophysical properties through
ical (PTMTC) functionalized with three carboxylic groups [143]. incorporation of lanthanide metal complexes in the framework,
This MOF has a 2D layer structure extending along the ab plane namely [Ba2 (H2 O)4 [LnL3 (H2 O)2 ](H2 O)n Cl] (L = 4,4 -disulfo-2,2 -
composed of a honeycomb structure. These layers stack by using bipyridine-N,N -dioxide, Ln = Sm, Eu, Gd, Tb, Dy) (Fig. 32). A
weak  and van der Waals interactions to form an open frame- stepwise approach was used and allowed for an examination of
work structure with hexagonal pores (Fig. 31a). It is even more the signicance of the ratio of metal to organic building units in
interesting that this material shows a reversible and highly selec- the preparation of a MOF containing lanthanide metal ions. By
tive solvent-induced shrinkingbreathing process involving large decreasing the ligand to metal ratio, a less dense, porous frame-
volume changes (2535%) that strongly inuence its magnetic work was prepared that maintained its luminescent characteristics.
properties (Fig. 31b). Thus, this magnetic sponge-like behavior Additionally, metalloligands were referred to as building units for
could be used as a new route towards magnetic solvent sensors. the development of lanthanide containing MOFs for use as sensing

Fig. 32. Lanthanide metal complex and structure of [Ba2 (H2 O)4 [LnL3 (H2 O)2 ](H2 O)n Cl] . Reproduced with permission from Ref. [147].
3060 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 33. Structure and luminescence properties of Zn3 L3 (DMF)2 (left) and Zn4 OL3 (right). Reproduced with permission from Ref. [150].

devices [148]. Proper selection of the linker is necessary to ade- work (Fig. 34a). Heating in air at different temperatures (180, 200,
quately shield the metal to prevent quenching of its luminescent 225, 250 C) for 1 day generated a series of dehydrated products.
properties. One of the dehydrated complexes was rehydrated when exposed
de Lill et al. [149] reported in 2007 the synthesis and photolumi- to H2 O vapor for 1 or 2 days. The solid-state luminescence spectra
nescent properties of a Eu MOF and a Eu/Tb mixed system MOF. In of these complexes (Fig. 34b and c) revealed that guest molecules
the mixed system, both Eu and Tb emissions were observed along removed/rehydrated from the MOF undoubtedly inuence the
with an increase in Eu emission intensity relative to the Eu MOF. This weak interactions between a ligand and a metal center. The work
has been attributed to the Eu being sensitized by both the organic provides a convenient and effective route for tuning emissions
linkers and the Tb. between UV and visible wavelengths by controlling the number of
guest molecules and may be useful for the design and fabrication
of multifunctional luminescent materials.
7.2.2. Luminescence in MOFs based on organic ligands
Two luminescent stilbene-based MOFs were prepared based
7.3. Sensors in MOFs
on trans-4,4 -stilbene dicarboxylic acid (LH2 ) and zinc nitrate in
two different solvents. A 2D network structure Zn3 L3 (DMF)2 was
The MOFs that possess luminescent properties together with
obtained in DMF, while a 3D porous framework structure Zn4 OL3
size- or shape-selective sorption properties can be used as sensing
resulted from DEF (Fig. 33) [150]. The optical properties of both
devices [146].
demonstrate that the LH2 organic ligand serves as the chromophore.
In both cases, the rigidity of the stilbene ligand increases upon
7.3.1. Sensors for selective ion monitoring
coordination to the metal center, resulting in increased emission
Recently, Chen et al. [153] reported a prototype luminescent
lifetimes for the MOF crystals as compared to solutions of trans-
MOF, Tb(BTC)G (MOF-76, G = guest solvent) (Fig. 35a). The lumines-
stilbene.
cence properties of the anion incorporated Tb(BTC)G (MOF-76b,
Studies have also been conducted with luminescent organic link-
G = methanol) microcrystalline solids were studied by immersing
ers, such as H2 hpbb as reported by Gndara et al. in 2007 [151]. As
Tb(BTC) in methanolic solutions of different concentrations of NaX
a ligand, hpbb emits a blue-white color under UV light, which is
(X = F , Cl , and Br ) and Na2 X (X = CO3 2 and SO4 2 ) (Fig. 35b).
slightly modied with the addition of different lanthanide metals,
The results show that the luminescence intensity of the anion
leading to the possible uses of these MOFs as diodes.
incorporated MOF-76b is signicantly increased, particularly for
the F incorporated MOF (Fig. 35c). The special properties under-
7.2.3. Luminescence based on guest molecules in MOFs lying the potential of MOF-76 for the recognition and sensing of
Huang et al. [152] reported a 3D porous MOF, anions exhibit a high-sensitivity sensing function with respect to
[Cd3 L6 ](BF4 )2 (SiF6 )(OH)2 13.5H2 O (L = 2,6-di(4-triazolyl)pyridine), the uoride anion.
in which the guest species in the open channels can be removed Chen et al. [154] recently reported the synthesis of luminescent
and reintroduced reversibly without destroying the porous frame- MOFs, [Eu(pdc)1.5 (dmf)](DMF)0.5 (H2 O)0.5 (1) (pdc = pyridine-3,5-

Fig. 34. (a) 3D framework of [Cd3 L6 ](BF4 )2 (SiF6 )(OH)2 13.5H2 O with the guest water molecules and anions in the cavities (SiF6 2 , polyhedron, blue; BF4 , space lling, green
and yellow); (b) Luminescence spectra of complexes with increasing dehydration, in the solid state at room temperature; (c) Luminescence spectra of complexes including
those partially rehydrated, in the solid state at RT. Reproduced with permission from Ref. [152].
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3061

Fig. 35. (a) Crystal X-ray structure of MOF-76b containing NaF with the model of uoride (green) at the center of the channel; (b) 5 D4 7 F5 transition intensities of MOF-76b
activated in different types of 102 M NaX and Na2 X methanol solution (excited and monitored at 353 and 548 nm, respectively); (c) Excitation (dotted) and PL spectra (solid)
of MOF-76b solid activated in different concentrations of NaF methanol solution (excited and monitored at 353 and 548 nm, respectively). Reproduced with permission from
Ref. [153].

Fig. 36. (a) Crystal X-ray structure of 1 with immobilized Lewis basic pyridyl sites oriented towards pore centers; (b) The excitation () and PL spectra (- - -) of solid 1b
activated in DMF solutions of Cu(NO3 )2 at different concentrations (excited and monitored at 321 and 618 nm, respectively); (c) Comparison of the luminescence intensity of
1b incorporating different metal ions, activated in 10 mm DMF solutions of M(NO3 )x . Adapted from Ref. [154].

dicarboxylate), with Lewis basic pyridyl sites for metal ion sensing and sensing of small molecules by using the specic properties of
(Fig. 36a). The luminescence characteristics of this MOF were stud- luminescent open Eu3+ sites.
ied as the pyridyl sites were coordinated to additional metal ions Using ultrasonic methods, Qiu et al. [156] obtained nanocrys-
introduced in a DMF solution (Fig. 36b). It was found that the tals of a uorescent microporous MOF, Zn3 (BTC)2 12H2 O (Fig. 38a),
identity of the additional metal ion is very signicant to the lumi- and quantitatively analyzed the signals of organoamines in an ace-
nescence capability of the complex, with alkali and alkaline earth tonitrile solution using uorescence spectrophotometric titrations.
metals having little effect on the luminescence while other metal Remarkable changes of emission intensity (uorescence quench-
ions, such as Cu2+ , cause signicant quenching (Fig. 36c). ing) were observed when the volume of ethylamine added into
acetonitrile was changed (Fig. 38b). This uorescence quenching
7.3.2. Sensors for the presence and/or types of guest/solvent suggests a high sensitivity to ethylamine and may lead to some
molecules highly sensitive sensors for organoamines.
Chen et al. [155] reported a rare earth microporous MOF of
Eu(BTC) (with open Eu3+ metal sites) (Fig. 38a). Within the MOF, 7.3.3. Sensors for stress-induced chemical detection
ethanol, acetone, dimethyl formamide, and other small molecules Besides sensors for anions and guest molecules, MOFs can also
exhibit different enhancing and quenching effects on the lumines- be used for stress-induced chemical detection. Recent work by
cence intensity (Fig. 37b and c). This MOF is suitable for the binding Allendorf et al. [157] demonstrated that the energy of molecular

Fig. 37. (a) Structure of Eu(BTC) MOF viewed along the c axis, and accessible Eu3+ sites are shown by the pink arrows. The PL spectra in the presence of various content of
(b) DMF and (c) acetone solvent, respectively (excited at 285 nm). Adapted from Ref. [155]. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of the article.)
3062 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 38. (a) Molecular-packing diagram of Zn3 (BTC)2 12H2 O viewed along the c axis; (b) Variation of emission spectra with the volume of ethylamine in 2 mL of acetonitrile
(excited at 327 nm). Reproduced with permission from Ref. [156].

adsorption can be converted to mechanical energy to create a highly 8. Drug storage and delivery in MOFs
responsive, reversible, and selective sensor by integrating a thin
lm of MOF HKUST-1 with a microcantilever surface (Fig. 39a). This 8.1. Introduction
sensor responds to water (Fig. 39b), methanol, and ethanol vapors,
but yields no response to either N2 or O2 . This is the rst report of The inability of conventional orally administered drugs to
the use of surface-enhanced Raman spectroscopy to characterize deliver medication at a controlled release rate has spawned much
the structure of a MOF lm. interest and research in novel methods for drug delivery. Developed
delivery systems include polymeric-based systems, liposome-
7.3.4. Sensors for anisotropic photoluminescence probes based systems, microporous zeolites, mesoporous silicon, and other
Harbuzaru et al. [158] presented new microporous Ln3+ -based mesoporous materials [159162]. Essentially, these different deliv-
materials, ITQMOF-1 and ITQMOF-2, based on the highly hydropho- ery routes are classied into organic systems and inorganic systems.
bic organic ligand Hpbb. These MOFs show no quenching of Organic systems benet from a wide array of biocompatibility, the
photoluminescence in the presence of water (Fig. 40a and b), ability to uptake many drugs, yet lack a controlled release mecha-
but a sharp decrease in photoluminescence in the presence of nism [163,164]. The inorganic delivery materials are able to deliver
ethanol enables them to be used to sense ethanol in both air the adsorbed drugs at a controlled rate due to their ordered porous
and water (Fig. 40c). It was also observed that the choice of network, but have a decreased loading capacity [165,166].
Ln3+ metal is signicant to the luminescent and magnetic prop-
erties of the MOFs. A ferromagnetic interaction between the 8.2. Drug-delivery methods
Tb3+ ions and a green emission in UV light was observed for
ITQMOF-1-Tb while ITQMOF-1-(5Eu95Gd) showed an antiferro- Uhrich et al. provide a complete review of the organic polymeric
magnetic interaction between Gd3+ and a red emission in UV light drug-delivery materials [167]. Most inorganic delivery materials
(Fig. 40d). have a mesoporous structure to allow for optimal uptake and deliv-

Fig. 39. (a) Verication of HKUST-1 on the microcantilever using SERS: (blue) SERS spectrum of HKUST-1 on a microcantilever; (red) SERS spectrum of an HKUST-1 lm on
a macroscopic substrate; (black) unenhanced Raman of a thick HKUST-1 layer used as a reference. Peaks labeled CH(Ar) correspond to out-of-plane aromatic CH bends;
(b) Temporal response of the cantilever piezoresistive sensor to water vapor diluted in N2 (room temperature, 1 atm). Reproduced with permission from Ref. [157]. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)
R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066 3063

Fig. 40. (a) Emission spectra of a ITQMOF-1-(5Eu95Gd) single crystal, recorded at room temperature and 10 K for two different orientations of the crystal relative to the
detector (red line: vertical, blue line: horizontal, excited at 290 nm). (b) Emission spectra of ITQMOF-2-Eu powder and single crystal (oriented in the vertical position), recorded
at room temperature (black line) and 10 K (green line). The inset shows an expansion of the 5 D0 7 F0 region at 10 K (excited at 290 nm). (c) Test for sensing capabilities of
the ITQMOF-1-Eu material. Variation of the uorescence signal intensity at 619 nm under alternating streams of air saturated with ethanol (signal intensity decreases) and
ethanol-free air (signal intensity increases). (d) [Gd, Eu]- and [Tb]-containing materials under UV light and interacting with a magnet. Adapted from Ref. [158].

ery of drugs (microporous materials usually do not possess large work [169]. To solve this problem, MOFs containing pores in the
enough apertures for useful drug delivery). Recently, Salonen et al. mesoporous range must be synthesized.
provided a review on the state of mesoporous silicon in drug deliv- Two such MOFs have been prepared by Horcajada et al. as MIL-
ery [160]. Zeolites in the mesoporous size range have also been 100 and MIL-101 [169]. These structures proved suitable for drug
studied for their application in drug delivery [161]. delivery due to their well-dened, ordered porosity. MIL-100 con-
tains pore diameters of 2529 with pentagonal window openings
8.2.1. Inorganic drug-delivery materials of 4.8 and hexagonal windows of 8.6 while MIL-101 possesses
MCM-41 is an inorganic material composed of siloxane bridges pore sizes of 2934 with a very large window opening of 12
with silanol groups available for interaction with guest species and for the pentagonal and 16 for the hexagonal windows [169]. MIL-
for better control of the size of the pore. It has been one of the most 100 was found to uptake 0.35 g ibuprofen/g dehydrated MIL-100
intensely studied inorganic compounds for drug delivery because whereas MIL-101 was able to uptake 1.4 g ibuprofen/g dehydrated
the pore walls allow for direct adsorption with no need for organic MIL-101. The difference can be explained by the size of ibupro-
functionalization [166,168]. Munoz et al. provided the necessary fen (6 10.3 ) which is able to t in both the pentagonal and
background research for drug delivery in mesoporous silicate with
their study of the release rate of ibuprofen in MCM-41 modied
with aminopropyl groups [165]. Their ndings established that the
release rate of ibuprofen in MCM-41 without the addition of func-
tional groups is independent of pore size so long as the mesoporous
opening is larger than the delivered drug. Complete delivery of the
drug occurs within two days. In addition, the functionalization of
MCM-41 with organic silane groups can impact the amount of drug
adsorbed, and therefore, the delivery rate [165].

8.2.2. MOF drug-delivery materials


As hybrid organicinorganic compounds, MOFs present them-
selves as optimal drug-delivery materials due to the adjustability of
the frameworks functional groups and the tunable pore size. With
MOFs, the benets of using organic materials (biocompatibility and
the ability to uptake large amounts of drugs) and inorganic mate-
rials (controlled release) may both be utilized. However, the main
drawback of using MOFs is that the small pore size, with diameters
that usually fall in the microporous range, limits the uptake and/or Fig. 41. The delivery rate of MIL-101, MIL-100, and MCM-41. Reproduced with per-
number of drug molecules that can be stored within the frame- mission from Ref. [3].
3064 R.J. Kuppler et al. / Coordination Chemistry Reviews 253 (2009) 30423066

Fig. 42. The breathing effect of MIL-53(Cr) upon adsorption and release at high temperature. Reproduced with permission from Ref. [9].

hexagonal windows of MIL-101, but not into the smaller pentagonal tuned by changing temperature or pressure. Another trend is
window of MIL-100 [3,169]. Desorption rates for MIL-101 exceeded the application of MOFs in a number of important industrial
that of MIL-100 by six days vs. three days, respectively. The initial applications such as methane purication and carbon dioxide
delivery mechanism consists of simple diffusion of weakly bonded sequestration.
molecules, whereas  interactions between the aromatic rings (4) The use of MOFs for size-, shape-, and enantio-selective catal-
and the ibuprofen are responsible for the elongated delivery times ysis may become one of the most promising applications. MOF
[169]. Fig. 41 compares the release rate of MIL-101, MIL-100, and catalysis is different from both homogenous catalysis and sur-
MCM-41, respectively. face heterogeneous catalysis. A reaction with known reactivity
In addition to MIL-100 and MIL-101, Loiseau et al. studied the and selectivity may behave very differently in a conned space
drug-delivery rate of MIL-53, a exible material known for its ability in a MOF.
to expand its structure upon heating in what is termed a breathing (5) In the last several years, new applications of MOFs, such as
effect (Fig. 42) [170]. MIL-53, with a maximum volume of approxi- those in the eld of porous magnets, luminescent sensors, drug
mately 1500 3 at high temperature and full expansion, was able to storage and delivery, and templated low-dimensional mate-
uptake approximately 20 wt% of ibuprofen with a complete delivery rial preparation, have been demonstrated. Breakthroughs in
taking approximately three weeks [9]. The long, steady delivery can the near future are possible with the continual development
be attributed to the exibility of the framework to bend around the of these applications.
ibuprofen molecules to maximize the bonding interactions while
still minimizing steric hindrance [9]. In conclusion, the MOF research community has made great
progress in the last decade, yet we may have just seen the tip of
8.3. Future work in drug delivery the iceberg in respect to the application potential of MOFs. Many
new types of applications will emerge as the research topic becomes
Although progress has been made, and MOFs have proven them- more and more popular. The future of the eld is indeed very bright.
selves suitable candidates for drug delivery, much research needs
to be done to realize the full potential of MOFs as materials for Appendix A. Supplementary data
drug delivery. With the increasing number of mesoporous MOFs
being synthesized, drug delivery utilizing MOFs show promising Supplementary data associated with this article can be found, in
potential. the online version, at doi:10.1016/j.ccr.2009.05.019.

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